Fiberglass Materials, Methods of Making, and Applications Thereof

ABSTRACT

Embodiments of the present invention described herein relate to fiberglass materials, composite glass materials, methods of making fiberglass materials and composite glass materials, and different applications of fiberglass materials and composite glass materials. The fiberglass materials can include a bimodal particle size distribution. The fiberglass materials can include an average aspect ratio of greater than about 2 to 1. Also described herein are composite glass materials including a first glass material and a second material. The second material can include at least one of post-consumer glass waste, fly ash, metakaolin, and slag. Also described herein are methods of making a composite glass material including providing a first glass material to a mixer; providing a second material to the mixer; and co-milling the first glass material and a second material to form a composite glass material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 62/203,245, filed on Aug. 10, 2015; U.S. Provisional PatentApplication Ser. No. 62/239,504, filed on Oct. 9, 2015; U.S. ProvisionalPatent Application Ser. No. 62/252,047, filed on Nov. 6, 2015; U.S.Provisional Patent Application Ser. No. 62/252,096, filed on Nov. 6,2015; and U.S. Provisional Patent Application Ser. No. 62/254,265, filedon Nov. 12, 2015, each of which is hereby incorporated by reference asthough fully set forth herein.

FIELD OF INVENTION

The present invention relates generally to fiberglass materials,composite glass materials, methods of making fiberglass materials andcomposite glass materials, and different applications of fiberglassmaterials and composite glass materials.

BACKGROUND

Glass fibers and related materials have been used to reinforce and actas fillers to various materials for many years. In some instances, glassfibers have been used to reinforce different materials or serve as afiller for different applications. For example, different materials havebeen used to reinforce concrete materials. Some materials are referredto generally as pozzolans. Pozzolans are a siliceous material that donot possess any cementing property but chemically react with calciumhydroxide (Ca(OH)₂) in the presence of water to form compounds havingcementitious properties.

Conventional pozzolans and fillers can have high costs of manufacturefor materials with certain desired functional properties or, on theother hand, have inferior mechanical or chemical properties at a lowercost of manufacture. Thus, there is a need for improved fiberglassmaterials that have sufficient mechanical or chemical properties thatcan be manufactured at a commercially acceptable cost.

SUMMARY

In one aspect, particulate fiberglass materials are provided herein. Insome embodiments, a waste fiberglass material can be reduced in size bydifferent operations. In some such embodiments, the fiberglass material,having been reduced in size, can have a bimodal particle sizedistribution. In some such embodiments, the fiberglass material, havingbeen reduced in size, can have an average aspect ratio of greater than 2to 1. In some embodiments, the waste fiberglass material can be sizedand formed into a powder form for use as a filler in differentapplications.

In another aspect, composite glass materials are provided herein. Insome embodiments, a composite glass material comprises a particulatefiberglass material and a second material. In some embodiments, theparticulate fiberglass material is co-milled with the second material toproduce the composite glass material. In other embodiments, theparticulate fiberglass material is mixed with the second material toproduce the composite glass material. In some embodiments, the secondmaterial of the composite glass material comprises at least one ofpost-consumer glass waste, fly ash, metakaolin, and slag. In someembodiments, the composite glass materials are suitable for use as afiller in different applications.

In another aspect, methods of making composite glass materials areprovided herein. In some embodiments, a method of making a compositeglass material comprises providing a first glass material to a mixer;providing a second material to the mixer; and co-milling the first glassmaterial and a second material to form a composite glass material.

In some embodiments, the second material comprises at least one ofpost-consumer glass waste, fly ash, metakaolin, and slag. In someembodiments, the second material comprises post-industrial waste glass.In some embodiments of the method, the second material comprises atleast one of soda lime glass, float glass, plate glass, and flat glass.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in a cement composition, an industrial and/orpaint filler composition, in a resin filler composition, or in anadhesive composition, among other applications.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a chart showing a results of particle size analysis forparticulate fiberglass material made according to an embodiment of thepresent invention.

FIG. 2 is an SEM image of particulate fiberglass material made accordingto an embodiment of the present invention.

FIG. 3 is an SEM image of particulate fiberglass material made accordingto an embodiment of the present invention.

FIG. 4 is a chart showing a results of particle size analysis forparticulate fiberglass material made according to an embodiment of thepresent invention.

FIG. 5 is a chart showing a results of particle size analysis forparticulate fiberglass material made according to an embodiment of thepresent invention.

FIG. 6 is a chart showing a co-milling operation for composite glassmaterial made according to an embodiment of the present invention.

DETAILED DESCRIPTION

The subject matter of embodiments of the present invention is describedhere with specificity to meet statutory requirements, but thisdescription is not necessarily intended to limit the scope of futureclaims. The subject matter to be claimed may be embodied in other ways,may include different elements or steps, and may be used in conjunctionwith other existing or future technologies. This description should notbe interpreted as implying any particular order or arrangement among orbetween various steps or elements except when the order of individualsteps or arrangement of elements is explicitly described. Theillustrative examples are given to introduce the reader to the generalsubject matter discussed herein and not intended to limit the scope ofthe disclosed concepts. The following sections describe variousadditional embodiments and examples with reference to the drawings inwhich like numerals indicate like elements and directional descriptionare used to describe illustrative embodiments but, like the illustrativeembodiments, should not be used to limit the present invention.

Unless indicated to the contrary, the numerical parameters set forth inthe following specification are approximations that can vary dependingupon the desired properties sought to be obtained by the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Moreover, all ranges disclosed hereinare to be understood to encompass any and all subranges subsumedtherein. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more, e.g. 1 to 6.1, and ending with amaximum value of 10 or less, e.g., 5.5 to 10. Additionally, anyreference referred to as being “incorporated herein” is to be understoodas being incorporated in its entirety.

It is further noted that, as used in this specification, the singularforms “a,” “an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

The present invention relates generally to fiberglass materials,composite glass materials, methods of making fiberglass materials andcomposite glass materials, and different applications of fiberglassmaterials and composite glass materials. Applications may include use incement compositions, industrial and paint compositions, resin fillercompositions, and adhesive compositions, among other applications.

For purposes herein, “composite glass materials” are materials having atleast one glass material, and at least one second material. The secondmaterial may be a second glass material or a non-glass material. Thecomposite glass material may, in some cases, be created by co-milling atleast one glass material with at least one second material or similaroperations, as described in detail below, or may be created by mixing atleast one glass material with at least one second material.

In some embodiments, the fiberglass materials can be manufactured fromdownchute waste generated during the manufacture of fiberglass. Thewaste fiberglass materials can be crushed, pulverized, milled, orotherwise sized such that the resulting fiberglass material comprises abimodal particle size distribution and/or an average aspect ratio ofgreater than 2 to 1. In some embodiments, the fiberglass materialscomprise a bimodal particle size distribution. The term “bimodal” refersto having or involving two modes, and particularly, having two distinctstatistical modes. In some embodiments, the resulting fiberglassmaterial comprises an average aspect ratio of greater than 2 to 1. Insome cases, the fiberglass material may be co-milled or mixed with othermaterials, as described in more detail below.

Persons of ordinary skill in the art will recognize that the presentinvention can be implemented in connection with the production,assembly, and application of a number of glass fibers. Non-limitingexamples of glass fibers and related waste material suitable for use inthe present invention can include those prepared from fiberizable glasscompositions such as “E-glass”, “A-glass”, “C-glass”, “S-glass”,“ECR-glass” (corrosion resistant glass), and fluorine and/or boron-freederivatives thereof. The composition of the glass material to befiberized is not generally important to the present invention, and assuch, embodiments of the present invention can be implemented inmanufacturing processes for any number of fiberizable glasscompositions.

Glass fibers can be formed from molten glass as will be discussed inmore detail below. For example, glass fibers can be formed in adirect-melt fiber forming operation or in an indirect, or marble-melt,fiber forming operation. In a direct-melt fiber forming operation, rawmaterials are combined, melted and homogenized in a glass meltingfurnace. The molten glass moves from the furnace to a forehearth andinto fiber forming apparatuses, such as bushings, where the molten glassis attenuated into continuous glass fibers. In a marble-melt glassforming operation, pieces or marbles of glass having the final desiredglass composition are preformed and fed into a bushing where they aremelted and attenuated into continuous glass fibers. If a premelter isused, the marbles are fed first into the premelter, melted, and then themelted glass is fed into a fiber forming apparatus, such as a bushing,where the glass is attenuated to form continuous fibers. For additionalinformation relating to glass compositions and methods of forming theglass fibers, see K. Lowenstein, The Manufacturing Technology ofContinuous Glass Fibres, (3d Ed. 1993), at pages 30-44, 47-103, and115-165, which are specifically incorporated by reference herein.

In a typical direct-melt fiber forming operation, a glass meltingfurnace and forehearth convey a stream of molten fiberizable material toan outlet fitted with a metallic bushing attached to the bottom of theforehearth. The molten glass flows from the bottom of the bushingthrough a large number of orifices or “tips” in a tip plate where theycan be attenuated by a winder to form glass filaments of desired size.The filaments can then be contacted with an applicator to apply a sizingcomposition, gathered by a guide to form a sliver or strand, and woundabout a collet of a winder. Examples of suitable sizing compositions andwinders are set forth in Loewenstein (supra) at pages 186-194 and237-287. As sizing compositions are generally applied after formation ofglass filaments, embodiments of the present invention can generally beimplemented in manufacturing processes where any number of sizingcompositions (or no sizing composition) are applied to the glassfilaments, and the present invention is not intended to be limited toany particular sizing composition. Similarly, the present invention isnot intended to be limited to manufacturing processes where anyparticular winder is used. As is known to those of skill in the art,winders are not required in all processes for forming fiberglassproducts as the glass fibers can be provided directly to otherprocessing equipment.

During the above-described manufacturing processes, industrial downchutewaste is generated during the fiber forming in the process. Downchutewaste refers to glass material that is not converted to a final finishedproduct and rejected as waste material during fiber forming. Sources ofdownchute waste can include waste from multiple locations in themanufacturing process as discussed further below. Typically, fiberglassmanufacturing generates as much as 10 to 15 percent downchute waste, andsometimes as much as 20 percent downchute waste. Typically, this wastematerial is discarded or disposed of in landfills due to difficulty andhigh costs of post-processing of the material. The result is millions ofpounds of downchute waste being sent to landfills each year in a typicalfiber glass manufacturing site.

Some embodiments of the present invention can utilize and recycle thedownchute waste fiberglass into different compositions useful indifferent applications. In some embodiments, the present inventionutilizes the downchute waste material to provide a fiberglass materialhaving properties advantageous for use in applications such as concreteor cement applications, industrial and paint filler applications, tilesand panel fillers, resin and material fillers, sealants and adhesives,and other uses. In some embodiments, the downchute glass may be mixedwith other filler materials such as post-consumer waste glass, fly ash,clays such as metakaolin, and/or blast furnace slag. In someembodiments, the downchute waste fiberglass may be co-milled with one ormore of these other filler materials.

I. Fiberglass Materials

In some embodiments, the waste fiberglass material can be reduced insize by different operations. In some such embodiments, the fiberglassmaterial, having been reduced in size, can have a bimodal particle sizedistribution. In some such embodiments, the fiberglass material, havingbeen reduced in size, can have an average aspect ratio of greater than 2to 1. In some embodiments, the waste fiberglass material can be sizedand formed into a powder form for use as a filler in differentapplications.

As provided above, the downchute waste material can include wastegenerated at different points in the manufacturing process. For example,downchute waste can include molten glass material that flows or dripsfrom the bottom of the bushing orifices or tips in a tip plate. Thedownchute waste can also include fiber breakouts that occur as the glassfilaments are attenuated by a winder. The downchute waste can alsoinclude glass fibers that have been wound about a spool, but arerejected, for example, due to the package being too small or not being afull spool of fiberglass or otherwise failing to meet manufacturingspecifications. One of ordinary skill in the art appreciates othersources of downchute glass material waste can be included withoutdeparting from this spirit and scope of the present invention.

Such downchute waste can include glass material having a consistentchemical composition that can provide predictable and advantageousproperties, for example, in use as a filler in different applications.For example, the downchute waste can comprise fiberizable glasscompositions characteristic of “E-glass”, “A-glass”, “C-glass”,“S-glass”, or “ECR-glass.”

In some embodiments, the downchute fiberglass waste material can becollected from the manufacturing operations and further processed toprovide a fiberglass material comprising a bimodal particle sizedistribution. In some embodiments, the downchute fiberglass wastematerial can be collected from the manufacturing operations and furtherprocessed to provide a fiberglass material comprising a plurality ofparticles having an average aspect ratio of greater than about 2 to 1.

In some embodiments, the downchute fiberglass waste material can bepulverized, crushed, or otherwise be processed by a sizing operation.Different pulverizing or sizing operations understood by one of ordinaryskill in the art can be utilized to generate the particulate fiberglassmaterial. For example, the pulverizing or sizing operation can includeat least one of chopping, grinding, crushing, shredding, cutting, andmilling. The pulverizing or sizing operation may include sub-operations,for example a shredding, sorting, grinding, drying, and/or other cuttingoperations. In some embodiments, the fiberglass waste material can becut or shredded to reduce the length of the fibers in the downchutewaste prior to being pulverized, crushed, or otherwise sized. In otherembodiments, the fiberglass waste material can be provided directly to apulverizing, crushing, or sizing operation without being cut to reducethe length of fibers.

In some embodiments, the particulate fiberglass material can becharacterized by a particle size distribution. The particulatefiberglass material having been reduced in size can comprise a bimodalparticle size distribution. In some embodiments, the particulatefiberglass material can comprise a bimodal particle size distributioncomprising a first mode having a particle size from about 5 microns toabout 30 microns and a second mode having a particle size from about 10microns to about 50 microns. In some embodiments, the particulatefiberglass material can comprise a bimodal particle size distributioncomprising a first mode having a particle size at about 4 microns and asecond mode having a particle size at about 10 microns. In otherembodiments, the particulate fiberglass material can comprise a bimodalparticle size distribution comprising a first mode having a particlesize at about 10 microns±50 microns and a second mode having a particlesize between about 400 microns±50 microns. In other embodiments, theparticulate fiberglass material can comprise a bimodal particle sizedistribution comprising a first mode having a particle size at about 100microns±50 microns and a second mode having a particle size betweenabout 400 microns±50 microns. In other embodiments, the particulatefiberglass material can comprise a bimodal particle size distributioncomprising a first mode having a particle size at about 150 microns±50microns and a second mode having a particle size between about 400microns±50 microns.

In other embodiments, the particulate fiberglass material can comprise abimodal particle size distribution comprising a first mode having aparticle size between about 1 micron to about 3 microns and a secondmode having a particle size between about 10 microns to about 12microns. In yet other embodiments, the particulate fiberglass materialcan comprise a bimodal particle size distribution comprising a firstmode having a particle size at about 6 microns to about 8 microns and asecond mode having a particle size between about 28 microns to about 32microns. In yet further embodiments, the particulate fiberglass materialcan comprise a bimodal particle size distribution comprising a firstmode having a particle size between about 4 microns to about 6 micronsand a second mode having a particle size between about 18 microns toabout 21 microns. In yet other embodiments, the particulate fiberglassmaterial can comprise a bimodal particle size distribution comprising afirst mode having a particle size at about 100 microns±50 microns and asecond mode having a particle size between about 400 microns±50 microns,as measured by cross-section Scanning Electron Microscopy (SEM), asdescribed more fully in Example 1, below.

In some embodiments, the particulate fiberglass material can have aparticle size of less than about 45 microns. In some embodiments, theparticulate fiberglass material can have a particle size of −325 mesh.In some embodiments, the particulate fiberglass material can have aparticle size of −400 mesh. In some embodiments, the particulatefiberglass material can have a particle size of less than about 1 mm.

In some embodiments, the particulate fiberglass material can comprise abimodal particle size distribution with between about 20% to 50% havinga particle size of less than about 5 microns and between about 20% toabout 50% having a particle size between about 10 microns to about 15microns. In some embodiments, the particulate fiberglass material cancomprise a bimodal particle size distribution with between about 20% to50% having a particle size of from about 5 microns to about 30 micronsand between about 20% to about 50% having a particle size from about 10microns to about 50 microns. In some embodiments, the particulatefiberglass material can comprise a bimodal particle size distributionhaving a first mode having a particle size of from about 5 microns toabout 30 microns and a second mode having a particle size from about 10microns to about 50 microns. In some embodiments, the particulatefiberglass material can comprise a bimodal particle size distributionwith between about 20% to 40% having a particle size of less than about1 microns and from about 20% to about 40% having a particle size fromabout 10 microns to about 15 microns.

In some embodiments, the particulate fiberglass material can becharacterized by its average aspect ratio. The aspect ratio refers tothe length of the particle divided by the diameter or width of theparticles. In some embodiments, the particulate fiberglass material canhave a high aspect ratio. In some embodiments, the particulatefiberglass material can have an average aspect ratio of greater than 2to 1. In some embodiments, the average aspect ratio of the particulatefiberglass material is greater than 2.5 to 1, and in some embodiments,greater than 3 to 1, and in some embodiments, greater than 4 to 1.

In some embodiments, the present invention comprises a method of makinga particulate fiberglass material. In some embodiments, the methodcomprises providing downchute fiberglass waste and reducing the size ofthe fiberglass waste to generate a particulate fiberglass material,wherein the particulate fiberglass material comprises a bimodal particlesize distribution. In some embodiments, the particulate fiberglassmaterial made according to methods described herein can have an averageaspect ratio of greater than 2 to 1. In some embodiments, theparticulate fiberglass material comprising a bimodal particle sizedistribution comprises a plurality of particles having an average aspectratio of greater than 2 to 1.

Turning to the figures, FIG. 1 is a bar graph of the particle sizedistribution of particulate fiberglass material for measurements from150 particles according to one embodiment. FIG. 2 is an SEM image at1,000× magnification of particulate fiberglass material according to oneembodiment. FIG. 3 is an SEM image particulate fiberglass material at10,000× magnification according to one embodiment. FIG. 4 shows thedistribution of a particle size analysis of particulate fiberglassmaterials having a bimodal particle size distribution prepared accordingto methods of embodiments of the present invention, as described furtherbelow in the Examples section. The first peak shown in FIG. 4 is about1.987 μm, and the second peak shown in FIG. 4 is about 8.06 μm. FIG. 5shows the distribution of a particle size analysis of particulatefiberglass materials having a bimodal particle size distributionprepared according to methods of embodiments of the present invention asdescribed further below in the Examples section.

II. Composite Glass Materials

In some embodiments, the downchute fiberglass waste material can beparticulate, crushed, or otherwise be processed by a sizing operation,as described herein. In some embodiments, the particulate fiberglassmaterial can be further processed and/or mixed with other materials tocreate a composite glass material.

In some embodiments, the particulate fiberglass material comprising abimodal particle size distribution further comprises a second material.In some embodiments, the particulate fiberglass material comprising abimodal particle size distribution is mixed with the second material. Insome embodiments, the particulate fiberglass material comprising abimodal particle size distribution is co-milled with the secondmaterial. In some embodiments, the particulate fiberglass materialcomprising a bimodal particle size distribution is co-milled with thesecond material, wherein the second material comprises at least one ofpost-consumer glass waste, fly ash, a natural clay, and slag.

In some embodiments, the particulate fiberglass material comprising aplurality of particles having an average aspect ratio of greater than 2to 1 further comprises a second material. In some embodiments, theparticulate fiberglass material a plurality of particles having anaverage aspect ratio of greater than 2 to 1 is mixed with the secondmaterial. In some embodiments, the particulate fiberglass material aplurality of particles having an average aspect ratio of greater than 2to 1 is co-milled with the second material. In some embodiments, theparticulate fiberglass material a plurality of particles having anaverage aspect ratio of greater than 2 to 1 is co-milled with the secondmaterial, wherein the second material comprises at least one ofpost-consumer glass waste, fly ash, a natural clay such as metakaolin,and slag.

In some embodiments, a composite glass material comprises a particulatefiberglass material and a second material. In some embodiments, theparticulate fiberglass material is co-milled with the second material toproduce the composite glass material. In other embodiments, theparticulate fiberglass material is mixed with the second material toproduce the composite glass material. In some embodiments, the secondmaterial of the composite glass material comprises at least one ofpost-consumer glass waste, fly ash, a natural clay such as metakaolin,and slag.

Certain aspects of the present invention will now be discussed inconnection with FIG. 6, which illustrates some embodiments of thepresent invention. Although the description associated with the Figurewill focus on embodiments shown in the Figure, it should be understoodthat only slight modifications need to be made to the components inorder to provide composite milled materials embodying the inventiveconcepts described in this application.

FIG. 6 shows a schematic block diagram of an exemplary method of makinga composite milled material. A glass material 1 is provided to a sizingoperation 10 where the first glass material is sorted and sized to apredetermined size. Different sizing operations understood by one ofordinary skill in the art can be utilized to generate a substantiallyuniform sized first glass material. For example, the sizing operation 10can include at least one of chopping, grinding, crushing, shredding,cutting, and milling. The sizing operation 10 may includesub-operations, for example a shredding, sorting, grinding, drying,and/or other cutting operations. The glass material can be provided aspost-industrial waste, for example as a downchute waste product that isfurther processed into a substantially uniform first glass material.After the sizing operation 10, the glass material proceeds to a inlinescale 20. Upon being weighed and further processed at the inline scale20, an amount of the glass material enters a mixer 40 where it is mixedwith a second glass material 2.

In some embodiments, the glass material 1 can be provided directly to amixer, for example, mixer 40, without any sizing operation. In some suchembodiments, the first glass material 1 can be downchute waste from afiberglass manufacturing operation that does not require any furthersizing operation prior to being provided to a mixer. In someembodiments, at the introduction to the mixer 40, the glass material canhave a particle size of greater than about 45 microns. In someembodiments, at the introduction to the mixer 40, the glass material canhave a particle size of +325 mesh. In some embodiments, at theintroduction to the mixer 40, the first material can have a particlesize of −1 inch mesh, and in some embodiments, a particle size of −¼inch mesh. In yet other embodiments, the glass material, for example, asdownchute waste glass, can be provided to the mixer at the size exitinga manufacturing operation. In yet other embodiments, the maximum size ofthe glass material can be determined by the dimensions of the downstreamequipment, for example, the mixer or the co-milling equipment.

A second material 2 is provided to the system. The second material 2 canbe sized, chopped, grinded, crushed, and/or sorted by techniques knownto those of ordinary skill in the art. In some embodiments, the secondmaterial 2 can be supplied to the process in a pre-sized form. Thesecond material 2 is provided to an inline scale 30. Upon being weighedand further processed at the inline scale 30, an amount of the secondmaterial enters the mixer 40.

In some embodiments, at the introduction to the mixer 40, the secondmaterial can have a particle size of greater than about 175 microns. Insome embodiments, at the introduction to the mixer 40, the secondmaterial can have a particle size of +80 mesh. In some embodiments, atthe introduction to the mixer 40, the second material can have aparticle size of −⅜ inch mesh. In yet other embodiments, the maximumsize of the second material can be determined by the dimensions of thedownstream equipment, for example, the mixer or the co-millingequipment.

The mixer 40 mixes the glass material and the second material to providea substantially uniform blend of the glass material and the secondmaterial. The substantially uniform blend of the glass material and thesecond material is then transferred to a milling operation 50. Themilling operation 50 co-mills the two starting materials to form asubstantially homogeneous composite. The milling operation 50 caninclude one milling operation or a plurality of milling operations. Forexample, the milling operation 50 can include at least one of an impactmiller, trough miller, air classification system, and other operationsknown to those of ordinary skill in the art. A composite glass material3 then exits the milling operation 50.

In some embodiments, the composite glass material 3 can have a particlesize of less than about 45 microns. In some embodiments, the compositeglass material 3 can have a particle size of −325 mesh. In someembodiments, the composite glass material 3 can have a particle size of−400 mesh.

One of ordinary skill in the art would understand that additionalequipment can be included to increase the throughputs necessary to meetany desired production levels.

The milling operation can co-mill different-sized glass materials andsecond materials. For example, in some embodiments, the millingoperation can co-mill a downchute waste fiberglass that has not beensized or chopped with a second material that has not been otherwisemilled, sized, or chopped. In other embodiments, the milling operationcan co-mill a downchute waste fiberglass that has been sized or choppedwith a second material that has not been otherwise milled, sized, orchopped. In yet other embodiments, the milling operation can co-mill adownchute waste fiberglass that has not been sized or chopped with asecond material that has been milled, sized, or chopped. In yet otherembodiments, the milling operation can co-mill a downchute wastefiberglass that has been sized or chopped with a second material thathas been sized or chopped. As one of ordinary skill in the art wouldunderstand, each of the starting materials can be sized or otherwiseprocessed (e.g., chopped, grinded, crushed, shredded, cut, and milled),or not sized or otherwise processed, prior to providing the startingmaterials to the system to form a composite glass material.

In some embodiments, the second material comprises pozzolanic materials,for example, but not to be considered limiting, post-consumer wasteglass, fly ash, clay materials such as metakaolin, and/or slag. In someembodiments, the second material is post-consumer waste glass material,for example soda lime glass. In some embodiments, the second materialcomprises at least one of soda lime glass, float glass, flat glass,plate glass, and CRT glass. In some embodiments, the second materialcomprises fly ash, metakaolin, or slag. The composite glass materialscomprising a fiberglass material and a second material are described inmore detail below.

A. A Fiberglass Material Co-Milled with Other Glass Waste

In some embodiments, the particulate fiberglass material can beprocessed and/or mixed with post-consumer glass waste, such as bottleglass, soda lime glass, optical glass, float glass, flat glass, plateglass, or CRT glass, to make up a filler material. In some embodiments,the particulate fiberglass material comprising a bimodal particle sizedistribution can be co-milled with a second material. In someembodiments, the particulate fiberglass material comprising an aspectratio greater than 2:1 can be co-milled with a second material. In otherembodiments, the particulate fiberglass material that is co-milled witha second material does not comprise a bimodal particle size distributionand/or does not comprise an aspect ratio greater than 2:1.

In some aspects, the composite glass material utilizes different wasteor recycled glass materials or siliceous materials with high alkalicontent, for example, nephylene syenite.

Some embodiments of the present invention can be characterized by thetotal amount of Na₂O present in the composite glass material. In someembodiments, the composite glass material of the present invention cancomprise between about 2.1 and about 8.2 weight percent Na₂O, and insome embodiments, between about 2.1 and about 8.0 weight percent Na₂O.Na₂O can be present, in some embodiments, in an amount between about 0.1and about 0.9 weight percent. In some embodiments, Na₂O can be presentin an amount between about 8.0 and about 18.5 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise between about 55 and about 70 weight percentSiO₂. SiO₂ can be present, in some embodiments, in an amount betweenabout 66.0 and about 88.0 weight percent. In some embodiments, SiO₂ canbe present in an amount between about 52.0 and about 60.0 weightpercent.

In some embodiments, the composite glass material of the presentinvention can comprise between about 5.0 and about 15.0 weight percentAl₂O₃. Al₂O₃ can be present, in some embodiments, in an amount betweentrace amounts and about 7.0 weight percent. In some embodiments, Al₂O₃can be present in an amount between about 10 and about 15 weightpercent.

In some embodiments, the composite glass material of the presentinvention can comprise between about 15 and about 20 weight percent CaO.CaO can be present, in some embodiments, in an amount between traceamounts and about 15.0 weight percent. In some embodiments, CaO can bepresent in an amount between about 21.0 and about 23.0 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise between about 1.0 and about 5.0 weight percentMgO. MgO can be present, in some embodiments, in an amount between about1.0 and about 3.0 weight percent. In some embodiments, MgO can bepresent in an amount between about 4.0 and about 5.0 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 0.4 weight percent K₂O. K₂O canbe present, in some embodiments, in an amount less than about 0.2 weightpercent. In some embodiments, K₂O can be present in an amount less thanabout 0.1 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 1.0 weight percent Fe₂O₃. Fe₂O₃can be present, in some embodiments, in an amount less than about 0.3weight percent. In some embodiments, Fe₂O₃ can be present in an amountless than about 0.5 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 0.12 weight percent Cr₂O₃. Cr₂O₃can be present, in some embodiments, in an amount less than about 0.10weight percent. In some embodiments, Cr₂O₃ can be present in an amountless than about 0.01 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 2.5 weight percent TiO₂. TiO₂ canbe present, in some embodiments, in an amount less than about 1.0 weightpercent. In some embodiments, TiO₂ can be present in an amount less thanabout 0.6 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 0.2 weight percent SO₃. SO₃ canbe present, in some embodiments, in an amount less than about 0.1 weightpercent. In some embodiments, SO₃ can be present in an amount less thanabout 0.01 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise between about 0.5 and about 2.0 weight percentB₂O₃. B₂O₃ can be present, in some embodiments, in an amount betweenabout 1.0 and about 2.0 weight percent. In some embodiments, B₂O₃ can bepresent in an amount between about 4.0 and about 6.0 weight percent. Insome embodiments, the composite glass material of the present inventioncan comprise less than about 0.5 weight percent SrO. SrO can be present,in some embodiments, in an amount less than about 0.3 weight percent.

In some embodiments, the composite glass material of the presentinvention can comprise less than about 0.5 weight percent BaO. BaO canbe present, in some embodiments, in an amount less than about 0.2 weightpercent. In some embodiments, the composite glass material of thepresent invention can comprise less than about 0.2 weight percent ZrO₂.ZrO₂ can be present, in some embodiments, in an amount less than about0.03 weight percent. In some embodiments, the composite glass materialcan include less than about 0.01 weight Cl. As one of ordinary skill inthe art would appreciate, the composite glass materials can includeimpurities and trace amounts of other materials. The composite glassmaterial can include various combinations of the above listed materialsat different amounts.

In some exemplary embodiments, the composite glass material comprisesabout 55 to about 70 weight percent SiO₂; about 5 to about 11 weightpercent Al₂O₃; about 15 to about 20 weight percent of CaO; about 1 to 3weight percent MgO; about 2.1 to about 8.0 weight percent Na₂O; and lessthan about 0.2 weight percent of K₂O.

In further embodiments, the composite glass material further comprisesless than about 0.3 weight percent Fe₂O₃; less than about 0.01 Cr₂O₃;less than about 0.6 weight percent TiO₂; less than about 0.1 weightpercent SO₃; about 0.5 to about 2.0 weight percent B₂O₃; less than about0.3 weight percent SrO; less than about 0.2 weight percent BaO; and lessthan about 0.03 weight percent ZrO₂.

In some embodiments, the composite glass material can include a widerrange of alkali within the material than conventional fillers. Forexample, conventional E-glass chemistry includes Na₂O levels less than 1weight percent. As another example, conventional soda lime glassincludes Na₂O levels greater than 8 weight percent. In certain aspects,the present invention includes a Na₂O level of between about 2.1 toabout 8.2 weight percent and exhibit properties characteristic ofE-glass chemistry but having a higher alkali content.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a first glass material into a mixer; providing a second glassmaterial into the mixer; and co-milling the first glass material and thesecond glass material to form a composite glass material.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a first glass material; chopping the first glass material;providing a second glass material; mixing the chopped first glassmaterial with the second glass material to provide a blend of thechopped first glass material and the second glass material; and millingthe blend of the chopped first glass material and the second glassmaterial to form a composite glass material.

In some embodiments, the method of making a composite glass materialcomprises making a composite glass material between about 2.1 to about8.2 weight percent of Na₂O, and in some embodiments, about between about2.1 to about 8.0 weight percent Na₂O. In some embodiments, the firstglass material is at least one of E-glass, A-glass, C-glass, D-glass,S-glass, and ECR-glass compositions. In some embodiments, the firstglass material is characterized as having an E-glass composition. Insome embodiments, the first glass material is industrial waste glass.

In some embodiments, the second glass material is at least one of sodalime glass, float glass, flat glass, plate glass, and CRT glass. In someembodiments, the second glass material is post-consumer waste glass. Insome embodiments, the second glass material comprises siliceousmaterials with high alkali content. In some embodiments, the secondglass material comprises nephylene syenite.

In certain aspects of the present invention, the composite glassmaterial can be used in concrete-related applications. In some suchapplications, the composite glass material can provide equivalent orimproved properties as compared to conventional pozzolans, such as, forexample, compressive strength activity index or shrinkage resistance.

Referring back to FIG. 6, the second glass material 2 is provided to thesystem. In some embodiments, the second glass material 2 ispost-consumer glass material, for example soda lime glass. In someembodiments, the second glass material comprises at least one of sodalime glass, float glass, flat glass, plate glass, and CRT glass. Thesecond glass material 2 can be sized, chopped, grinded, crushed, and/orsorted by techniques known to those of ordinary skill in the art. Insome embodiments, the second glass material 2 can be supplied to theprocess at in pre-sized form. The second glass material 2 is provided toa inline scale 30. Upon being weighed and further processed at theinline scale 30, an amount of the second glass material enters the mixer40.

In some embodiments, at the introduction to the mixer 40, the secondglass material can have a particle size of greater than about 175microns. In some embodiments, at the introduction to the mixer 40, thesecond glass material can have a particle size of +80 mesh. In someembodiments, at the introduction to the mixer 40, the second glassmaterial can have a particle size of −⅜ inch mesh. In yet otherembodiments, the maximum size of the second glass material can bedetermined by the dimensions of the downstream equipment, for example,the mixer or the co-milling equipment.

The mixer 40 mixes the first glass material and the second glassmaterial to provide a substantially uniform blend of the first glassmaterial and the second glass material. The substantially uniform blendof the first glass material and the second glass material is thentransferred to a milling operation 50. The milling operation 50 co-millsthe two starting materials to form a substantially homogeneouscomposite. The milling operation 50 can include one milling operation ora plurality of milling operations. For example, the milling operation 50can include at least one of an impact miller, trough miller, airclassification system, and other operations known to those of ordinaryskill in the art. A composite glass material 3 then exits the millingoperation 50.

In some embodiments, the composite glass material 3 can have a particlesize of less than about 45 microns. In some embodiments, the compositeglass material 3 can have a particle size of −325 mesh. In someembodiments, the composite glass material 3 can have a particle size of−400 mesh.

One of ordinary skill in the art would understand that additionalequipment can be included to increase the throughputs necessary to meetany desired production levels.

The milling operation can co-mill different-sized first glass materialsand second glass materials. For example, in some embodiments, themilling operation can co-mill a downchute waste fiberglass that has notbeen sized or chopped with a second glass material that has not beenotherwise sized or chopped. In other embodiments, the milling operationcan co-mill a downchute waste fiberglass that has been sized or choppedwith a second glass material that has not been otherwise sized orchopped. In yet other embodiments, the milling operation can co-mill adownchute waste fiberglass that has not been sized or chopped with asecond glass material that has been sized or chopped. In yet otherembodiments, the milling operation can co-mill a downchute wastefiberglass that has been sized or chopped with a second glass materialthat has been sized or chopped. As one of ordinary skill in the artwould understand, each of the starting materials can be sized orotherwise processed (e.g., chopped, grinded, crushed, shredded, cut, andmilled), or not sized or otherwise processed, prior to providing thestarting materials to the system to form a composite glass material.

Conventional filler products utilizing post-consumer glass waste,including waste glass sometimes referred to as soda lime glass or bottleglass, can have certain disadvantages as compared to some embodiments ofthe present invention. For example, post-consumer bottle glass caninclude high alkali content that may help reduce alkali silicatereactions in a pozzolan-reinforcement application. However, thelong-term viability of structures with high amounts of alkalis withinthe conventional pozzolans may problematic as the high alkali contentmay weaken the structure integrity of the associated concrete structuresand accelerate or exacerbate the mechanical failure of the concretestructure. In an industrial and paint filler application, conventionalpozzolans using post-consumer bottle glass can have high variability inthe chemistry and color of the glass stock used. In some conventionalapplications, the inherent variation in the conventional post-consumermilled glass can lead to problems controlling tint or hiding, which mayaffect the “whiteness” level of certain paint products.

The composite glass material according to certain aspects describedherein may provide a viable alternative to pozzolans with high alkalicontent and pozzolans with purely E-glass chemistry. In some aspects,the composite glass material can comprise a composition that includes asufficiently high silica and alumina content necessary to drive apozzolanic reaction, but contains amounts of other components retrievedfrom other waste glass sources that can offset costs while aid intargeting specific performance requirements. For example, the compositeglass materials according to embodiments described herein can provideimproved workability, improved water tightness, improved resistance toadverse chemical reactions, higher mechanical strength, increaseddurability, decreased permeability, reduced sulfate attack, reducedshrinkage, reduced volume, reduced heat of hydration, reduced alkalisilicate reactions, and reduced segregation. In some embodiments, theseproperties can be achieved through use of the composite glass materialsdescribed herein at a lower cost than conventional pozzolans by usingdifferent waste glass materials. Embodiments of the present inventioncan achieve full pozzolanic reactivity without the potentiallydetrimental outcome that may arise from usage of glass with high alkali,for example, in concrete.

In certain aspects of the present invention, the composite glassmaterial can be used in concrete-related applications. In some suchapplications, the composite glass material can provide equivalent orimproved properties as compared to conventional pozzolans, such as, forexample, compressive strength activity index, shrinkage resistance.

B. A Fiberglass Material Co-Milled with a Fly Ash Material

In some embodiments, the composite glass material is made from at leastone of a post-industrial waste material, for example, a fly ashmaterial. The fly ash material includes by-products of burning coal inan electrical generating station. In some embodiments, the fly ashmaterial can be classified as Class F, Class C, or Class N as set forthin the specifications provided in ASTM C618.

In some embodiments, the composite glass material can be used as afiller product for use in concrete or cement applications, industrialand paint filler applications, tiles and panel fillers, resin andmaterial fillers, sealants and adhesives, and other uses.

Some embodiments of the present invention can be characterized by thetotal amount of SiO₂, Al₂O₃, and Fe₂O₃ present in the composite glassmaterial. In some embodiments, the composite glass material of thepresent invention can comprise between about 50 weight percent and about85 weight percent SiO₂, Al₂O₃, and Fe₂O₃. The total amount of SiO₂,Al₂O₃, and Fe₂O₃ can be present, in some embodiments, in an amountbetween about 40 weight percent to about 50 weight percent. In someembodiments, the total amount of SiO₂, Al₂O₃, and Fe₂O₃ can be presentin an amount between about 50 weight percent to about 75 weight percentof the total composite glass material.

In some embodiments, the composite glass material of the presentinvention can comprise between about 6.0 weight percent and about 28weight percent CaO. CaO can be present, in some embodiments, in anamount between about 6.5 weight percent to about 21.5 weight percent. Insome embodiments, CaO can be present in an amount between about 10.0weight percent to about 20.0 weight percent of the total composite glassmaterial. In some embodiments, CaO can be present in an amount betweenabout 15.0 weight percent to about 28.0 weight percent of the totalcomposite glass material.

In some embodiments, the composite glass material of the presentinvention can comprise between about 0.5 weight percent and about 5.0weight percent MgO, and in some embodiments, between about 0.1 weightpercent and about 5.0 weight percent MgO. MgO can be present, in someembodiments, in an amount between about 0.8 weight percent to about 4.0weight percent. In some embodiments, MgO can be present in an amountbetween about 1.0 weight percent to about 3.5 weight percent of thetotal composite glass material. In some embodiments, MgO can be presentin an amount between about 2.0 weight percent to about 5.0 weightpercent of the total composite glass material.

In some embodiments, the composite glass material of the presentinvention can comprise between about 0.1 weight percent to about 2.5weight percent SO₃. SO₃ can be present, in some embodiments, betweenabout 0.1 weight percent to about 2.0 weight percent. In someembodiments, SO₃ can be present between about 0.1 weight percent toabout 1.5 weight percent of the total composite glass material.

In some embodiments, the composite glass material of the presentinvention can comprise between about 0.1 weight percent to about 18.0weight percent of total alkali content. The total alkali content caninclude Na₂O and K₂O. The total alkali content, in some embodiments, cancomprise between about 0.1 weight percent to about 2.0 weight percent.In some embodiments, the total alkali content can be between about 2.1weight percent to about 8.2 weight percent of the total composite glassmaterial. As one of ordinary skill in the art would appreciate, thecomposite glass materials can include impurities and trace amounts ofother materials. The composite glass material can include variouscombinations of the above listed materials at different amounts.

In some exemplary embodiments, the composite glass material comprisesabout 50 to about 85 weight percent of SiO₂, Al₂O₃, and Fe₂O₃; about 6to about 28 weight percent of CaO; about 0.1 to 5 weight percent MgO;about 0.1 to about 2.5 weight percent SO₃; and a total alkali contentbetween about 0.1 to about 18 weight percent.

In some exemplary embodiments, the composite glass material comprisesabout 50 to about 85 weight percent of SiO₂, Al₂O₃, and Fe₂O₃; about 15to about 28 weight percent of CaO; about 2 to 5 weight percent MgO;about 0.1 to about 2.5 weight percent SO₃; and a total alkali contentbetween about 0.1 to about 18 weight percent.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a first glass material into a mixer; providing a fly ashmaterial into the mixer; and co-milling the first glass material and thefly ash material to form a composite glass material.

In some embodiments, the first glass material and the fly ash materialcan be supplied to the mixer in a ratio of about 90 percent by weight offirst glass material to about 10 percent by weight of the fly ashmaterial. In other embodiments, the first glass material and the fly ashmaterial can be supplied to the mixer in a ratio of about 50 percent byweight of first glass material to about 50 percent by weight of the flyash material. In yet other embodiments, the first glass material and thefly ash material can be supplied to the mixer in a ratio of about 75percent by weight of first glass material to about 25 percent by weightof the fly ash material. In some embodiments, the first glass materialand the fly ash material can be supplied to the mixer in a range ofratios between about 9:1 to about 1:1 by weight, between about 4:1 toabout 1:1 by weight, and between about 3:1 to about 2:1 by weight. Insome embodiments, the first glass material and the fly ash material canbe supplied to the mixer at a ratio of about 9:1 by weight, about 8:1 byweight, about 7:1 by weight, about 6:1 by weight, about 5:1 by weight,about 4:1 by weight, about 3:1 by weight, about 2:1 by weight, and about1:1 by weight.

In some embodiments, the first glass material and the fly ash materialcan be supplied to the mixer in a ratio of about 10 percent by weight offirst glass material to about 90 percent by weight of the fly ashmaterial. In other embodiments, the first glass material and the fly ashmaterial can be supplied to the mixer in a ratio of about 33 percent byweight of first glass material to about 67 percent by weight of the flyash material. In yet other embodiments, the first glass material and thefly ash material can be supplied to the mixer in a ratio of about 25percent by weight of first glass material to about 75 percent by weightof the fly ash material. In some embodiments, the fly ash material andthe first glass material can be supplied to the mixer in a range ofratios between about 9:1 to about 1:1 by weight, between about 4:1 toabout 1:1 by weight, and between about 3:1 to about 2:1 by weight. Insome embodiments, the fly ash material and the first glass material canbe supplied to the mixer at a ratio of about 9:1 by weight, about 8:1 byweight, about 7:1 by weight, about 6:1 by weight, about 5:1 by weight,about 4:1 by weight, about 3:1 by weight, and about 2:1 by weight.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a first glass material; chopping the first glass material;providing a fly ash material; mixing the chopped first glass materialwith the fly ash material to provide a blend of the chopped first glassmaterial and the fly ash material; and milling the blend of the choppedfirst glass material and the fly ash material to form a composite glassmaterial.

In some embodiments, the first glass material can be sized or chopped(prior to introduction to a mixer or a co-milling operation) to have aparticle size of greater than about 45 microns. In some embodiments, thefirst glass material can be sized or chopped to have a particle size of+325 mesh. In some embodiments, the first glass material can have aparticle size of −1 inch mesh, and in some embodiments, a particle sizeof −¼ inch mesh. In some embodiments, the first glass material is atleast one of E-glass, A-glass, C-glass, D-glass, S-glass, and ECR-glasscompositions. In some embodiments, the first glass material ischaracterized as having an E-glass composition. In some embodiments, thefirst glass material is post-industrial waste glass.

In some embodiments, the fly ash material can have (prior tointroduction to a mixer or a co-milling operation) a mean particle sizerange between of 12 microns and 150 microns.

In some embodiments, the fly ash material comprises by-products ofburning coal in an electrical generating station. In some embodiments,the fly ash material can be classified as Class F, Class C, or Class Naccording to the specifications provided in ASTM C618.

In some embodiments, the method of making a composite glass materialcomprises making a composite glass material having between about 50 andabout 85 weight percent SiO₂, Al₂O₃, and Fe₂O₃.

In some exemplary embodiments, the method of making a composite glassmaterial comprises making a composite glass material having betweenabout 50 to about 85 weight percent of SiO₂, Al₂O₃, and Fe₂O₃; about 6.0to about 28 weight percent of CaO; about 0.5 to 5 weight percent MgO;about 0.1 to about 2.5 weight percent SO₃; and a total alkali contentbetween about 0.1 to about 18 weight percent.

In some embodiments, the method of making a composite glass materialcomprises making a composite glass material having between about 50 toabout 85 weight percent of SiO₂, Al₂O₃, and Fe₂O₃; about 15 to about 28weight percent of CaO; about 2 to 5 weight percent MgO; about 0.1 toabout 2.5 weight percent SO₃; and a total alkali content between about0.1 to about 2 weight percent.

In some embodiments in a concrete or cementitious application, thecomposite glass material can have any one or more of the followingadvantages: can be manufactured at a lower net manufacturing cost ascompared to milled fiber glass; can provide better alkali silicatereaction performance than milled post-consumer bottled glass; cansatisfy a greater filler volume in concrete over for example,metakaolins and other clays which results in a lower amount of cement ina concrete structure; and/or can provide superior workability over otherpozzolans and cement alone.

C. A Fiberglass Material Co-Milled with a Clay Material

In some embodiments, the composite glass material comprises at least oneof a natural clay material, for example, metakaolin. Metakaolin is adehydroxylate form of the clay mineral kaolinite. Kaolinite is minedfrom high purity kaolin deposits or from kaolinite deposits or tropicalsoils of lower purity. It may also isolated from paper sludge waste oroil sand tailings. Metakaolin has a high water uptake in concretehydration, which detracts from the workability of concrete blended withmetakaolin. The co-milled metakaolin and glass composite reduces thewater absorbing capacity of the concrete, resulting in improvedworkability of the concrete.

In some embodiments, the composite glass material can be used as afiller product for use in concrete or cement applications, industrialand paint filler applications, tiles and panel fillers, resin andmaterial fillers, sealants and adhesives, and other uses.

Some embodiments of the present invention can be characterized by thetotal amount of clay product present in the composite glass material. Insome embodiments, the composite glass material of the present inventioncan comprise between about 50 weight percent and about 85 weight percentmetakaolin. The metakaolin can be present, in some embodiments, in anamount between about 40 weight percent to about 50 weight percent. Insome embodiments, metakaolin can be present in an amount between about50 weight percent to about 75 weight percent of the total compositeglass material. In some embodiments, metakaolin can be present in anamount between about 25 weight percent to about 50 weight percent of thetotal composite glass material.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a glass material into a mixer; providing a metakaolin materialinto the mixer; and co-milling the glass material and the metakaolinmaterial to form a composite glass material.

In some embodiments, the glass material and the metakaolin material canbe supplied to the mixer in a ratio of about 90 percent by weight ofglass material to about 10 percent by weight of the metakaolin material.In other embodiments, the glass material and the metakaolin material canbe supplied to the mixer in a ratio of about 50 percent by weight ofglass material to about 50 percent by weight of the metakaolin material.In yet other embodiments, the glass material and the metakaolin materialcan be supplied to the mixer in a ratio of about 75 percent by weight ofglass material to about 25 percent by weight of the metakaolin material.In some embodiments, the glass material and the metakaolin material canbe supplied to the mixer in a range of ratios between about 9:1 to about1:1 by weight, between about 4:1 to about 1:1 by weight, and betweenabout 3:1 to about 2:1 by weight. In some embodiments, the glassmaterial and the metakaolin material can be supplied to the mixer at aratio of about 9:1 by weight, about 8:1 by weight, about 7:1 by weight,about 6:1 by weight, about 5:1 by weight, about 4:1 by weight, about 3:1by weight, about 2:1 by weight, and about 1:1 by weight.

In some embodiments, the glass material and the metakaolin material canbe supplied to the mixer in a ratio of about 10 percent by weight ofglass material to about 90 percent by weight of the metakaolin material.In other embodiments, the glass material and the metakaolin material canbe supplied to the mixer in a ratio of about 33 percent by weight ofglass material to about 67 percent by weight of the metakaolin material.In yet other embodiments, the glass material and the metakaolin materialcan be supplied to the mixer in a ratio of about 25 percent by weight ofglass material to about 75 percent by weight of the metakaolin material.In some embodiments, the metakaolin material and the glass material canbe supplied to the mixer in a range of ratios between about 9:1 to about1:1 by weight, between about 4:1 to about 1:1 by weight, and betweenabout 3:1 to about 2:1 by weight. In some embodiments, the metakaolinmaterial and the glass material can be supplied to the mixer at a ratioof about 9:1 by weight, about 8:1 by weight, about 7:1 by weight, about6:1 by weight, about 5:1 by weight, about 4:1 by weight, about 3:1 byweight, and about 2:1 by weight.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a glass material; chopping the glass material; providing ametakaolin material; mixing the chopped first glass material with themetakaolin material to provide a blend of the chopped glass material andthe metakaolin material; and milling the blend of the chopped glassmaterial and the metakaolin material to form a composite glass material.

In some embodiments, the glass material can be sized or chopped (priorto introduction to a mixer or a co-milling operation) to have a particlesize of greater than about 45 microns. In some embodiments, the glassmaterial can be sized or chopped to have a particle size of +325 mesh.In some embodiments, the glass material can have a particle size of −1inch mesh, and in some embodiments, a particle size of −¼ inch mesh. Insome embodiments, the glass material is at least one of E-glass,A-glass, C-glass, D-glass, S-glass, and ECR-glass compositions. In someembodiments, the glass material is characterized as having an E-glasscomposition. In some embodiments, the glass material is post-industrialwaste glass.

In some embodiments, the metakaolin material can have (prior tointroduction to a mixer or a co-milling operation) a mean particle sizerange between of 0.1 microns and 15 microns.

In some embodiments, the method of making a composite glass materialcomprises making a composite glass material having between about 50 andabout 85 weight percent metakaolin. In some embodiments in a concrete orcementitious application, the composite milled glass material can haveany one or more of the following advantages: can be manufactured at alower net manufacturing cost as compared to milled fiber glass; canprovide better chemical and/or erosion resistance; and/or can providesuperior workability over other pozzolans and cement alone.

D. A Fiberglass Material Co-Milled with a Slag Material

In some embodiments, the composite glass material is made from at leastone of a waste product of metal refining material, for example, a slagmaterial. Slag is a glassy substance comprising Ca—Al—Mg silicates, andis by-product of metal smelting, such as iron smelting. The exactchemical composition of the slag varies depending on the raw materialsused in the production process. For example, a granular slag is obtainedwhen molten iron slag from a blast furnace is quenched with steam orwater. The granular slag may be milled or otherwise ground to a finepowder that is called ground-granulated blast furnace glass (GGBS). Insome embodiments, a slag material may be mixed or co-milled withdownchute glass to produce a composite glass material. Concreteformulated with the composite glass material comprising slag hasimproved chemical and corrosion resistance compared to concreteformulated with slag alone.

Some embodiments of the present invention can be characterized by thetotal amount of slag product present in the composite glass material. Insome embodiments, the composite glass material of the present inventioncan comprise between about 50 weight percent and about 85 weight percentslag. The slag can be present, in some embodiments, in an amount betweenabout 40 weight percent to about 50 weight percent. In some embodiments,slag can be present in an amount between about 50 weight percent toabout 75 weight percent of the total composite glass material. In someembodiments, slag can be present in an amount between about 25 weightpercent to about 50 weight percent of the total composite glassmaterial.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a glass material into a mixer; providing a slag material intothe mixer; and co-milling the glass material and the slag material toform a composite glass material.

In some embodiments, the glass material and the slag material can besupplied to the mixer in a ratio of about 90 percent by weight of glassmaterial to about 10 percent by weight of the slag material. In otherembodiments, the glass material and the slag material can be supplied tothe mixer in a ratio of about 50 percent by weight of glass material toabout 50 percent by weight of the slag material. In yet otherembodiments, the glass material and the slag material can be supplied tothe mixer in a ratio of about 75 percent by weight of glass material toabout 25 percent by weight of the slag material. In some embodiments,the glass material and the slag material can be supplied to the mixer ina range of ratios between about 9:1 to about 1:1 by weight, betweenabout 4:1 to about 1:1 by weight, and between about 3:1 to about 2:1 byweight. In some embodiments, the glass material and the slag materialcan be supplied to the mixer at a ratio of about 9:1 by weight, about8:1 by weight, about 7:1 by weight, about 6:1 by weight, about 5:1 byweight, about 4:1 by weight, about 3:1 by weight, about 2:1 by weight,and about 1:1 by weight.

In some embodiments, the glass material and the slag material can besupplied to the mixer in a ratio of about 10 percent by weight of glassmaterial to about 90 percent by weight of the slag material. In otherembodiments, the glass material and the slag material can be supplied tothe mixer in a ratio of about 33 percent by weight of glass material toabout 67 percent by weight of the slag material. In yet otherembodiments, the glass material and the slag material can be supplied tothe mixer in a ratio of about 25 percent by weight of glass material toabout 75 percent by weight of the slag material. In some embodiments,the slag material and the glass material can be supplied to the mixer ina range of ratios between about 9:1 to about 1:1 by weight, betweenabout 4:1 to about 1:1 by weight, and between about 3:1 to about 2:1 byweight. In some embodiments, the slag material and the glass materialcan be supplied to the mixer at a ratio of about 9:1 by weight, about8:1 by weight, about 7:1 by weight, about 6:1 by weight, about 5:1 byweight, about 4:1 by weight, about 3:1 by weight, and about 2:1 byweight.

In some embodiments, the present invention comprises a method of makinga composite glass material. In some embodiments, the method comprisesproviding a glass material; chopping the glass material; providing aslag material; mixing the chopped first glass material with the slagmaterial to provide a blend of the chopped glass material and the slagmaterial; and milling the blend of the chopped glass material and theslag material to form a composite glass material.

In some embodiments, the glass material can be sized or chopped (priorto introduction to a mixer or a co-milling operation) to have a particlesize of greater than about 45 microns. In some embodiments, the glassmaterial can be sized or chopped to have a particle size of +325 mesh.In some embodiments, the glass material can have a particle size of −1inch mesh, and in some embodiments, a particle size of −¼ inch mesh. Insome embodiments, the glass material is at least one of E-glass,A-glass, C-glass, D-glass, S-glass, and ECR-glass compositions. In someembodiments, the glass material is characterized as having an E-glasscomposition. In some embodiments, the glass material is post-industrialwaste glass.

In some embodiments, the slag material can have (prior to introductionto a mixer or a co-milling operation) a mean particle size range betweenof 0.1 microns and 15 microns. In some embodiments, the method of makinga composite glass material comprises making a composite glass materialhaving between about 50 and about 85 weight percent slag.

III. Downchute Glass Having Bimodal Particle Size with Second Material

In some embodiments, the fiberglass material having a bimodal particlesize distribution may be co-milled with other filler materials such aspost-consumer waste glass such as post-consumer glass waste, fly ash,clays such as metakaolin, and/or blast furnace slag to form a compositeglass material.

In some embodiments, the fiberglass material having a bimodal particlesize distribution may be mixed (specifically without co-milling) with asecond material such as post-consumer waste glass such as post-consumerglass waste, fly ash, metakaolin, and/or blast furnace slag to form afiller material. In some embodiments, the glass material and the secondmaterial can be supplied to the mixer in a ratio of about 10 percent byweight of glass material to about 90 percent by weight of the slagmaterial. In other embodiments, the glass material and the secondmaterial can be supplied to the mixer in a ratio of about 33 percent byweight of glass material to about 67 percent by weight of the secondmaterial. In yet other embodiments, the glass material and the secondmaterial can be supplied to the mixer in a ratio of about 25 percent byweight of glass material to about 75 percent by weight of the secondmaterial. In some embodiments, the second material and the glassmaterial can be supplied to the mixer in a range of ratios between about9:1 to about 1:1 by weight, between about 4:1 to about 1:1 by weight,and between about 3:1 to about 2:1 by weight. In some embodiments, thesecond material and the glass material can be supplied to the mixer at aratio of about 9:1 by weight, about 8:1 by weight, about 7:1 by weight,about 6:1 by weight, about 5:1 by weight, about 4:1 by weight, about 3:1by weight, and about 2:1 by weight.

IV. Downchute Glass Having Aspect Ratio with Second Material

In some embodiments, the fiberglass material having an aspect ratio ofgreater than 2 to 1 may be co-milled with other filler materials such aspost-consumer waste glass such as post-consumer glass waste, fly ash,clays such as metakaolin, and/or blast furnace slag to form a compositeglass material.

In some embodiments, the fiberglass material having an aspect ratio ofgreater than 2 to 1 may be mixed (specifically without co-milling) withother filler materials such as post-consumer waste glass such aspost-consumer glass waste, fly ash, clays such as metakaolin, and/orblast furnace slag.

V. Applications of Fiberglass Materials and Composite Glass Materials

In some embodiments, the particulate fiberglass material having abimodal distribution, the particulate fiberglass material having anaspect ratio of greater than 2 to 1 (collectively called “milled glassmaterials”), and the composite glass materials described above, can beutilized as a filler product for use in concrete or cement applications,industrial and paint filler applications, tiles and panel fillers, resinand material fillers, sealants and adhesives, and other uses.

In some embodiments, a cement composition comprises a particulatefiberglass material having a bimodal distribution. In some embodiments,an industrial and paint composition comprises a particulate fiberglassmaterial having a bimodal distribution. In some embodiments, a resinfiller composition comprises a particulate fiberglass material having abimodal distribution. In some embodiments, an adhesive comprises aparticulate fiberglass material having a bimodal distribution.

In some embodiments, a cement composition comprises a particulatefiberglass material having a bimodal distribution co-milled with atleast one of post-consumer glass waste, fly ash, a natural clay such asmetakaolin, and slag. In some embodiments, an industrial and paintcomposition comprises a particulate fiberglass material having a bimodaldistribution co-milled with at least one of post-consumer glass waste,fly ash, a natural clay such as metakaolin, and slag. In someembodiments, a resin filler composition comprises a particulatefiberglass material having a bimodal distribution co-milled with atleast one of post-consumer glass waste, fly ash, a natural clay such asmetakaolin, and slag. In some embodiments, an adhesive comprises aparticulate fiberglass material having a bimodal distribution co-milledwith at least one of post-consumer glass waste, fly ash, a natural claysuch as metakaolin, and slag.

In some embodiments, a cement composition comprises a particulatefiberglass material having an average aspect ratio of greater than about2 to 1. In some embodiments, an industrial and paint compositioncomprises a particulate fiberglass material having an average aspectratio of greater than about 2 to 1. In some embodiments, a resin fillercomposition comprises a particulate fiberglass material having anaverage aspect ratio of greater than about 2 to 1. In some embodiments,an adhesive comprises a particulate fiberglass having an average aspectratio of greater than about 2 to 1.

In some embodiments, a cement composition comprises a particulatefiberglass material having an average aspect ratio of greater than about2 to 1 co-milled with at least one of post-consumer glass waste, flyash, a natural clay, and slag. In some embodiments, an industrial andpaint composition comprises a particulate fiberglass material having anaverage aspect ratio of greater than about 2 to 1 co-milled with atleast one of post-consumer glass waste, fly ash, a natural clay such asmetakaolin, and slag. In some embodiments, a resin filler compositioncomprises a particulate fiberglass material having an average aspectratio of greater than about 2 to 1 co-milled with at least one ofpost-consumer glass waste, fly ash, a natural clay such as metakaolin,and slag. In some embodiments, an adhesive comprises a particulatefiberglass material having an average aspect ratio of greater than about2 to 1 co-milled with at least one of post-consumer glass waste, flyash, a natural clay such as metakaolin, and slag.

In some embodiments, any suitable fiberglass material is co-milled witha second material. In some embodiments, the second material comprises atleast one of post-consumer glass waste, fly ash, a natural clay such asmetakaolin, and slag. In some embodiments, a cement compositioncomprises a fiberglass material co-milled with at least one ofpost-consumer glass waste, fly ash, a natural clay such as metakaolin,and slag. In some embodiments, an industrial and paint compositioncomprises a fiberglass co-milled with at least one of post-consumerglass waste, fly ash, a natural clay such as metakaolin, and slag. Insome embodiments, a resin filler composition comprises a fiberglassmaterial co-milled with at least one of post-consumer glass waste, flyash, a natural clay such as metakaolin, and slag. In some embodiments,an adhesive comprises a fiberglass material co-milled with at least oneof post-consumer glass waste, fly ash, a natural clay such asmetakaolin, and slag.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in a concrete or cementitious application. In somesuch embodiments, the fiberglass materials and/or composite glassmaterials can comprise about 5 to about 40 weight percent of a cementcomposition. The fiberglass materials and/or composite glass materialscan be present, in some embodiments, in an amount between about 10weight percent and 35 weight percent of a cement composition. In someembodiments, the fiberglass materials and/or composite glass materialscan be present in an amount between about 10 weight percent and 30weight percent of a cement composition. The cement composition using thefiberglass materials and/or composite glass materials can bemanufactured using unit operations known to those of ordinary skill inthe art.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in an industrial or paint filler application. Insome such embodiments, the fiberglass materials and/or composite glassmaterials can comprise about 5 to about 40 weight percent or about 5 toabout 30 weight percent of an industrial or paint filler. The fiberglassmaterials and/or composite glass materials can be present, in someembodiments, in an amount between about 7 weight percent and 30 weightpercent of an industrial or paint filler. In some embodiments, thefiberglass materials and/or composite glass materials can be present inan amount between about 10 weight percent and 20 weight percent of anindustrial or paint filler. The industrial or paint fillers using thefiberglass materials and/or composite glass materials can bemanufactured using unit operations known to those of ordinary skill inthe art.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in a tile or panel application. In some suchembodiments, the fiberglass materials and/or composite glass materialscan comprise about 0.5 to about 20.0 weight percent of a tile or panelfiller. The fiberglass materials and/or composite glass materials can bepresent, in some embodiments, in an amount between about 0.5 weightpercent and 30.0 weight percent of a tile or panel filler. In someembodiments, the fiberglass materials and/or composite glass materialscan be present in an amount between about 10.0 weight percent and 40.0weight percent of a tile or panel filler. The tile or panel fillersusing the fiberglass materials and/or composite glass materials can bemanufactured using unit operations known to those of ordinary skill inthe art.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in a resin and material filler application. Insome such embodiments, the fiberglass materials and/or composite glassmaterials can comprise about 5.0 to about 20.0 weight percent of a resinand material filler. The fiberglass materials and/or composite glassmaterials can be present, in some embodiments, in an amount betweenabout 5.0 weight percent and 30.0 weight percent of a resin and materialfiller. The resin and material fillers using the fiberglass materialsand/or composite glass materials can be manufactured using unitoperations known to those of ordinary skill in the art.

In some embodiments, the fiberglass materials and/or composite glassmaterials can be used in a sealant or adhesive application. In some suchembodiments, the fiberglass materials and/or composite glass materialscan comprise about 2.0 to about 15.0 weight percent of a sealant oradhesive filler. The fiberglass materials and/or composite glassmaterials can be present, in some embodiments, in an amount betweenabout 1.0 weight percent and 20.0 weight percent of a sealant oradhesive filler. In some embodiments, the fiberglass materials and/orcomposite glass materials can be present in an amount between about 5.0weight percent and 30.0 weight percent of a sealant or adhesive filler.The sealant and adhesive filler using the fiberglass materials and/orcomposite glass materials can be manufactured using unit operations.

In certain aspects of the present invention, fiberglass materials and/orcomposite glass materials can be used in industrial and paint-fillerapplications. In some such applications, fiberglass materials and/orcomposite glass materials can provide equivalent or improved propertiesas compared to conventional fillers, such as, for example, consistentchemistry of the filler, consistent color, higher flattening efficiency,improved refractive index, or thermal stability within a crystallinesilica free product. In some embodiments, fiberglass materials and/orcomposite glass materials can be manufactured at lower cost. In someembodiments in industrial or paint filler application, fiberglassmaterials and/or composite glass materials can provide capacity for LEEDcredits and points by use of at least one post-industrial waste orby-product.

EXAMPLE 1 Particulate Fiberglass Materials

Non-limiting embodiments of particulate fiberglass materials wereprepared according to some embodiments of the present invention. In oneexample, the particulate fiberglass materials were made from TEXOtreated E-glass fibers and were analyzed to determine particle size ofthe material. The particulate fiberglass material was analyzed using aFEI Quanta 250 FEG-SEM with a 20 KV accelerating voltage and spot size3. Images were collected at 1,000× to capture the distribution of thelarger particles and 10,000× to capture the distribution of the smallerparticles. The average particle size is 5.38 μm±5.22 μm. FIG. 1 showsthe distribution of 150 measurements. FIG. 2 shows an SEM image at1,000× magnification. FIG. 3 shows an SEM image at 10,000×magnification.

Other non-limiting embodiments of particulate fiberglass materialshaving a bimodal particle size distribution were prepared according tosome embodiments of the present invention. FIG. 4 shows the distributionof a particle size analysis of particulate fiberglass materials having abimodal particle size distribution prepared according to methods ofembodiments of the present invention. The first peak shown in FIG. 4 isabout 1.987 μm, and the second peak shown in FIG. 4 is about 8.06 μm.The aspect ratio of exemplary particles of such particulate fiberglassmaterial was calculated. Table 1 provides the results of measurements ofthe particles:

TABLE 1 Measured Particles Width Calculated Particle # Length (μm) (μm)Aspect Ratio 1 29.02 3.00 9.67 2 26.63 3.00 8.88 3 46.17 4.12 11.21 452.55 3.16 16.63 5 36.35 3.61 10.07 6 59.91 3.16 18.96 7 37.48 1.4126.58 8 69.53 2.24 31.04 9 32.02 2.83 11.31 10 26.02 3.00 8.67 11 28.792.24 12.85 12 48.01 3.16 15.19 13 33.42 2.83 11.81 14 41.00 3.16 12.9715 50.33 2.24 22.47 16 37.01 4.24 8.73 17 34.44 4.24 8.12 18 40.50 2.0020.25 19 39.05 3.16 12.36 20 56.86 4.24 13.41

Other non-limiting embodiments of particulate fiberglass materialshaving a bimodal particle size distribution were prepared according tosome methods of the present invention. FIG. 5 shows the distribution ofa particle size analysis of particulate fiberglass materials having abimodal particle size distribution prepared according to methods ofembodiments of the present invention.

EXAMPLE 2 Composite Glass Materials

Non-limiting embodiments of composite glass materials were preparedaccording to some embodiments of the present invention. In one example,the particulate fiberglass materials were made from TEXO treated E-glassfibers composite glass materials were prepared by co-milling with asecond material according to Table 2, with the two comparative examplescontaining 100% fly ash from two different sources. Inductively CoupledPlasma Optical Emission Spectroscopy (ICP-OES) was used to determine therelative oxides content of the samples, as shown in Table 3. In somecases, using post-consumer glass waste as the second material results ina composite glass material having a Na₂O content of greater than 2weight percent, based on the weight of the composite glass material. Insome cases, using fly ash as the second material results in a compositeglass material having a Fe₂O₃ content of greater than 2 weight percent,based on the weight of the composite glass material.

TABLE 2 Sample Composition Sample: E glass (wt %) Bottle Glass (wt %)Fly Ash (wt %) 1 85 15 2 90 10 3 50 50 Comparative 1 100 Comparative 2100

TABLE 3 Oxides Content Sample: Al₂O₃ (wt %) Fe₂O₃ (wt %) Na₂O (wt %)SiO₂ (wt %) 1 na¹ na 3.14, 3.21 na 2 13.0, 12.8 0.944, 0.937 na 53.5,54.3 3 16.6, 16.1 3.59, 3.46 na 52.0, 51.5 Comp. 1 16.4, 16.1 11.4, 11.3na 48.1, 47.5 Comp. 2 18.3, 17.6 10.9, 11.2 na 43.2, 41.7

It is to be understood that the present description illustrates aspectsof the various embodiments of the invention relevant to a clearunderstanding of the invention. Certain aspects of the invention thatwould be apparent to those of ordinary skill in the art and that,therefore, would not facilitate a better understanding of the inventionhave not been presented in order to simplify the present description.Although the present invention has been described in connection withcertain embodiments, the present invention is not limited to theparticular embodiments disclosed, but is intended to cover modificationsthat are within the spirit and scope of the invention.

That which is claimed:
 1. A particulate fiberglass material comprising abimodal particle size distribution.
 2. The particulate fiberglassmaterial of claim 1, wherein the bimodal particle size distributioncomprises a first mode having a particle size from about 5 microns toabout 30 microns and a second mode having a particle size from about 10microns to about 50 microns.
 3. The particulate fiberglass material ofclaim 1, wherein the bimodal particle size distribution comprises afirst mode having a particle size at about 100 microns±50 microns and asecond mode having a particle size between about 400 microns±50 microns.4. The particulate fiberglass material of claim 1, comprising aplurality of particles having an average aspect ratio of greater thanabout 2 to
 1. 5. A cement composition comprising the particulatefiberglass material of claim
 1. 6. An industrial and paint compositioncomprising the particulate fiberglass material of claim
 1. 7. A resinfiller composition comprising the particulate fiberglass material ofclaim
 1. 8. An adhesive composition comprising the particulatefiberglass material of claim
 1. 9. A filler composition comprising theparticulate fiberglass material of claim
 1. 10. The particulatefiberglass material of claim 1, further comprising a second material.11. The particulate fiberglass material of claim 10, wherein theparticulate fiberglass material is co-milled with the second material.12. The particulate fiberglass material of claim 10, wherein the secondmaterial comprises at least one of post-consumer glass waste, fly ash,metakaolin, and slag.
 13. A cement composition comprising theparticulate fiberglass material of claim
 12. 14. An industrial and paintcomposition comprising the particulate fiberglass material of claim 12.15. A resin filler composition comprising the particulate fiberglassmaterial of claim
 12. 16. An adhesive composition comprising theparticulate fiberglass material of claim
 12. 17. A particulatefiberglass material comprising a plurality of particles having anaverage aspect ratio of greater than about 2 to
 1. 18. The particulatefiberglass material of claim 17, comprising a plurality of particleshaving a bimodal particle size distribution.
 19. A cement compositioncomprising the particulate fiberglass material of claim
 17. 20. Anindustrial and paint composition comprising the particulate fiberglassmaterial of claim
 17. 21. A resin filler composition comprising theparticulate fiberglass material of claim
 17. 22. An adhesive compositioncomprising the particulate fiberglass material of claim
 17. 23. Theparticulate fiberglass material of claim 17, further comprising a secondmaterial.
 24. The particulate fiberglass material of claim 23, whereinthe particulate fiberglass material is co-milled with the secondmaterial.
 25. The particulate fiberglass material of claim 23, whereinthe second material comprises at least one of post-consumer glass waste,fly ash, metakaolin, and slag.
 26. A cement composition comprising theparticulate fiberglass material of claim
 24. 27. An industrial and paintcomposition comprising the particulate fiberglass material of claim 24.28. A resin filler composition comprising the particulate fiberglassmaterial of claim
 24. 29. An adhesive composition comprising theparticulate fiberglass material of claim
 24. 30. A composite glassmaterial comprising a particulate fiberglass material and a secondmaterial.
 31. The composite glass material of claim 30, wherein theparticulate fiberglass material is co-milled with the second material.32. The composite glass material of claim 31, wherein the secondmaterial comprises at least one of post-consumer glass waste, fly ash,metakaolin, and slag.
 33. A cement composition comprising the compositeglass material of claim
 32. 34. An industrial and paint compositioncomprising the composite glass material of claim
 32. 35. A resin fillercomposition comprising the composite glass material of claim
 32. 36. Anadhesive composition comprising the composite glass material of claim32.